DE19918997C2 - Process for operating a plant for steam reforming of hydrocarbons, in particular methanol, and corresponding plant - Google Patents

Process for operating a plant for steam reforming of hydrocarbons, in particular methanol, and corresponding plant

Info

Publication number
DE19918997C2
DE19918997C2 DE19918997A DE19918997A DE19918997C2 DE 19918997 C2 DE19918997 C2 DE 19918997C2 DE 19918997 A DE19918997 A DE 19918997A DE 19918997 A DE19918997 A DE 19918997A DE 19918997 C2 DE19918997 C2 DE 19918997C2
Authority
DE
Germany
Prior art keywords
water vapor
reforming reactor
mixture
temperature
plant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
DE19918997A
Other languages
German (de)
Other versions
DE19918997A1 (en
Inventor
Matthias Wolfsteiner
Stefan Brauchle
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mercedes Benz Fuel Cell GmbH
Original Assignee
Xcellsis AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xcellsis AG filed Critical Xcellsis AG
Priority to DE19918997A priority Critical patent/DE19918997C2/en
Priority to JP2000613560A priority patent/JP3782665B2/en
Priority to PCT/EP2000/001225 priority patent/WO2000064576A1/en
Priority to DE50013776T priority patent/DE50013776D1/en
Priority to EP00906329A priority patent/EP1173274B1/en
Publication of DE19918997A1 publication Critical patent/DE19918997A1/en
Application granted granted Critical
Publication of DE19918997C2 publication Critical patent/DE19918997C2/en
Priority to US09/984,339 priority patent/US7377950B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006—Controlling or regulating processes
    • B01J19/0013—Controlling the temperature of the process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J12/00—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor
    • B01J12/007—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor in the presence of catalytically active bodies, e.g. porous plates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • C01B3/58—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
    • C01B3/583—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction the reaction being the selective oxidation of carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00054—Controlling or regulating the heat exchange system
    • B01J2219/00056—Controlling or regulating the heat exchange system involving measured parameters
    • B01J2219/00058—Temperature measurement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00186—Controlling or regulating processes controlling the composition of the reactive mixture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00191—Control algorithm
    • B01J2219/00193—Sensing a parameter
    • B01J2219/00195—Sensing a parameter of the reaction system
    • B01J2219/00202—Sensing a parameter of the reaction system at the reactor outlet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00191—Control algorithm
    • B01J2219/00211—Control algorithm comparing a sensed parameter with a pre-set value
    • B01J2219/00213—Fixed parameter value
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00191—Control algorithm
    • B01J2219/00222—Control algorithm taking actions
    • B01J2219/00227—Control algorithm taking actions modifying the operating conditions
    • B01J2219/00229—Control algorithm taking actions modifying the operating conditions of the reaction system
    • B01J2219/00231—Control algorithm taking actions modifying the operating conditions of the reaction system at the reactor inlet
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0435—Catalytic purification
    • C01B2203/044—Selective oxidation of carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/047—Composition of the impurity the impurity being carbon monoxide

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Description

Die vorliegende Erfindung betrifft ein Verfahren zum Betrieb einer Anlage zur Wasserdampfreformerierung von Kohlenwasser­ stoffen, insbesondere Methanol nach dem Oberbegriff des Patentanspruchs 1 sowie eine entsprechende Anlage nach dem Oberbegriff des Patentanspruchs 4.The present invention relates to a method of operation a plant for the steam reforming of hydrocarbons substances, especially methanol according to the preamble of Claim 1 and a corresponding system according to Preamble of claim 4.

Mit derartigen Verfahren werden beispielsweise mobile Anlagen zur Wasserdampfreformierung von Methanol in brennstoffzellen­ betriebenen Kraftfahrzeugen betrieben, um Wasserstoff für die Speisung der Brennstoffzellen zu gewinnen.With such methods, for example, mobile systems for steam reforming of methanol in fuel cells motor vehicles operated to produce hydrogen for the Win fuel cell supply.

Zum Betrieb derartiger Anlagen ist es bekannt, die in einen Reformierungsreaktor eingeleitete Menge an aufbereitetem Wasserdampf/Methanol-Gemisch abhängig vom Lastzustand der Anlage variabel einzustellen. In der DE-AS 19 49 184 und der DE 21 57 722 C2 ist zu diesem Zwecke, mit der Modifikation, daß dort Methan anstelle von Methanol verwendet wird, eine Strahl­ pumpe vorgesehen, deren Dampfdurchfluß in Abhängig von dem Lastzustand der Anlage eingestellt wird, wodurch sich bei Last­ wechsel auch der Methanzufluß entsprechend der Strahlpumpen­ charakteristik ändert. Aus der DE 196 23 937 C1 ist es bekannt, das Wasserdampf/Methanol-Mischungsverhältnis des in einen Re­ formierungsreaktor eingeleiteten Wasserdampf/Methanol-Gemisches unbeeinflußt von kurzzeitigen Lastwechselvorgängen auf einem vorgebbaren Sollwert zu halten. Dies vermeidet unerwünschte, kurzzeitige Erhöhungen der CO-Konzentration im Reformat auf­ grund eines zu geringen Wasseranteils im Wasserdampf/Methanol- Gemisch. Eine Sensorik bzw. eine Steuer- oder Regeleinheit zur Regelung des Wasserdampf/Methanol-Mischungsverhältnisses auf den Sollwert ist hierbei stromaufwärts von dem Reformierungs­ reaktor angeordnet.For the operation of such systems, it is known that in one Reforming reactor initiated amount of processed Water vapor / methanol mixture depending on the load condition of the System adjustable. In DE-AS 19 49 184 and DE 21 57 722 C2 is for this purpose, with the modification that there methane is used instead of methanol, a beam pump provided, the steam flow depending on the Load state of the system is set, which changes under load also change the methane inflow according to the jet pumps characteristic changes. From DE 196 23 937 C1 it is known the water vapor / methanol mixing ratio of the in a Re Formation reactor initiated steam / methanol mixture unaffected by short-term load changes on one to maintain a predefinable setpoint. This avoids unwanted brief increases in the CO concentration in the reformate due to too little water in the steam / methanol  Mixture. A sensor system or a control unit for Regulation of the water vapor / methanol mixing ratio the setpoint is upstream of the reforming arranged reactor.

Aus der DE 196 23 919 C1 ist ein Verfahren zum Betrieb einer Anlage zur Wasserdampfreformierung von Methanol bekannt, bei welchem das Wasserdampf/Methanol-Mischungsverhältnis des in den Reformierungsreaktor eingeleiteten Wasserdampf/Methanol- Gemisches abhängig vom Lastzustand und/oder Laständerungen der Anlage derart eingestellt wird, daß eine über den gesamten Lastbereich hinweg gleichbleibende CO-Konzentration im Reformat erhalten wird. Ein Sensor, mittels dessen die Steuer- oder Regeleinheit ein den Lastzustand beschreibendes Signal erhält, ist hierbei stromabwärts von dem Reformierungsreaktor angeordnet.DE 196 23 919 C1 describes a method for operating a Plant known for steam reforming of methanol, at which is the water vapor / methanol mixing ratio of the in the Reforming reactor introduced water vapor / methanol Mixture depending on the load condition and / or load changes of the System is set so that one over the entire Consistent CO concentration in the reformate throughout the load range is obtained. A sensor by means of which the control or Control unit receives a signal describing the load state, is downstream of the reforming reactor arranged.

Aus einer noch unveröffentlichten Patentanmeldung der Anmelde­ rin (DE 198 47 211) ist schließlich ein Verfahren zum Betreiben einer Vorrichtung zur Erzeugung von wasserstoffreichem Gas be­ kannt, bei welchem eine katalytische Wasserdampfreformierung eines Wasserstoff/Brennstoff-Gemisches unter Zufuhr von Wärme­ energie in einem Reformer durchgeführt wird, und in einer CO- Oxidationsstufe eine selektive katalytische Oxidation von Kohlenmonoxid aus dem wasserstoffreichen Gas durchgeführt wird, wobei eine Übertragung von Wärmeenergie aus der CO-Oxidations­ stufe in den Reformer stattfindet. Bei diesem Verfahren wird vor oder in der CO-Oxidationsstufe ein sauerstoffhaltiges Gas in einer vorgegebenen Menge zum Gasgemischstrom zugeführt, wobei die Menge des zugeführten sauerstoffhaltigen Gases in Abhängigkeit von der Temperatur des Gasgemischstromes am Ausgang der Reformer/CO-Oxidationsstufe eingestellt wird.From an as yet unpublished patent application rin (DE 198 47 211) is a method of operation a device for generating hydrogen-rich gas knows in which a catalytic steam reforming of a hydrogen / fuel mixture with the supply of heat energy is carried out in a reformer and in a CO Oxidation stage a selective catalytic oxidation of Carbon monoxide is carried out from the hydrogen-rich gas being a transfer of thermal energy from the CO oxidation stage in the reformer takes place. With this procedure an oxygen-containing gas before or in the CO oxidation stage supplied to the gas mixture stream in a predetermined amount, where the amount of the supplied oxygen-containing gas in Dependence on the temperature of the gas mixture flow on Output of the reformer / CO oxidation level is set.

Sämtlichen beschriebenen Verfahren ist gemeinsam, daß die vorgesehenen Regelungsmaßnahmen im wesentlichen das Problem betreffen, einen möglichst gleichmäßigen Betrieb einer Anlage zur Wasserdampfreformierung auch bei dynamischen Lastwechseln zur Verfügung zu stellen. Eine Langzeitregelung, welche alterungsbedingte Änderungen der Charakteristika der Reaktor­ komponenten berücksichtigt, ist mit diesen Maßnahmen nicht möglich.All of the described methods have in common that the proposed regulatory measures essentially the problem concern the smoothest possible operation of a system for steam reforming even with dynamic load changes  to provide. A long-term regulation, which age-related changes in the characteristics of the reactor components is not taken into account with these measures possible.

Aufgabe der Erfindung ist daher eine möglichst einfache und unaufwendige Langzeitregelung eines Reformierungsreaktors.The object of the invention is therefore a simple and uncomplicated long-term regulation of a reforming reactor.

Diese Aufgabe wird gelöst durch ein Verfahren mit den Merkmalen des Patentanspruchs 1 sowie eine Anlage mit den Merkmalen des Patentanspruchs 4.This problem is solved by a method with the features of claim 1 and a system with the features of Claim 4.

Durch Steuerung der Eduktzusammensetzung, d. h. des Wasser/Koh­ lenwasserstoff-Verhältnisses, ist es in einfacher Weise möglich alterungsbedingten Änderungen der Wirksamkeit bzw. der Funk­ tionsfähigkeit der Reaktorkomponenten, insbesondere eine alterungsbedingten Verschiebung des Temperaturprofils im Reaktorbett, entgegenzusteuern. Durch Erhöhung des Wasser­ anteils erhält man am Eintritt einer einem Reformer nachge­ schalteten CO-Oxidationsstufe eine höhere CO-Konzentration, wodurch ein insgesamt gleichmäßigeres Temperaturprofil erreicht wird. Hierdurch kann in wirksamer Weise einer Alterung des Reformers bzw. des CO-Oxidators entgegengewirkt werden.By controlling the starting material composition, i.e. H. of water / Koh hydrogen ratio, it is possible in a simple manner age-related changes in effectiveness or radio ability of the reactor components, in particular a age-related shift of the temperature profile in the Reactor bed to counteract. By increasing the water a portion is given to a reformer at the time of entry switched CO oxidation level a higher CO concentration, whereby an overall more uniform temperature profile is achieved becomes. This can effectively age the Reformer or the CO oxidizer can be counteracted.

Vorteilhafte Ausgestaltungen der Erfindung sind Gegenstand der Unteransprüche.Advantageous embodiments of the invention are the subject of Subclaims.

Gemäß einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird das Mischungsverhältnis des Wasserdampf/Koh­ lenwasserstoff-Gemisches in Abhängigkeit von der Temperatur T des aus dem Reformierungsreaktor austretenden Gasstroms eingestellt. Eine derartige Temperatur ist in einfacher Weise feststellbar und in zuverlässiger Weise einem in dem Reformie­ rungsreaktor herrschenden Temperaturprofil zuordnenbar.According to a preferred embodiment of the invention The mixing ratio of water vapor / Koh Hydrogen-hydrogen mixture depending on the temperature T of the gas stream emerging from the reforming reactor set. Such a temperature is simple ascertainable and reliable one in the reformie Rung reactor prevailing temperature profile assignable.

Zweckmäßigerweise wird die Temperatur des aus dem Reformie­ rungsreaktor austretenden Gasstroms mittels der Einstellung des Wasserstoff/Kohlenwasserstoff-Mischungsverhältnisses auf einen konstanten Wert geregelt. Hierdurch ist es in einfacher Weise möglich, die Reformierungsparameter des Reformierungsreaktors über eine sehr lange Zeitdauer konstant zu halten.Conveniently, the temperature of the reformie tion reactor emerging gas stream by adjusting the  Hydrogen / hydrocarbon mixture ratio to one constant value regulated. This makes it simple possible the reforming parameters of the reforming reactor to keep constant over a very long period of time.

Gemäß einer bevorzugten Ausführungsform der erfindungsgemäßen Anlage weist diese stromabwärtig des Reformierungsreaktors angeordnete Mittel zur Bestimmung der Temperatur des aus dem Reformierungsreaktor austretenden Gasstroms und eine Steuer- und Regeleinheit zur Beaufschlagung der Gemischbereitungsstufe, über welche ein geeignetes Wasserdampf/Kohlenwasserstoff- Mischverhältnis einstellbar ist, auf. Hierbei führt die Steuer- und Regeleinheit die Steuerung der Gemischbereitungsstufe unter Verwendung der durch die Mittel zur Bestimmung der Temperatur bestimmten Temperatur durch.According to a preferred embodiment of the invention The plant has this downstream of the reforming reactor arranged means for determining the temperature of the Reforming reactor emerging gas stream and a control and control unit for loading the mixture preparation stage, through which a suitable water vapor / hydrocarbon Mixing ratio is adjustable. Here the tax and control unit to control the mixture preparation stage Use of the temperature determining means certain temperature.

Die Erfindung wird nun anhand der beigefügten Zeichnung weiter erläutert. In dieser zeigt:The invention will now be further elucidated on the basis of the attached drawing explained. In this shows:

Fig. 1 ein schematisches, stark vereinfachtes Blockdia­ gramm einer Anlage zur Wasserdampfreformierung von Methanol. Fig. 1 is a schematic, greatly simplified Blockdia program of a plant for steam reforming of methanol.

Die in Fig. 1 nur mit ihren vorliegend relevanten Komponenten gezeigte Anlage zur Wasserdampfreformierung von Methanol ist beispielsweise in einem brennstoffzellenbetriebenen Kraftfahr­ zeug einsetzbar, um Wasserstoff für die Speisung der Brenn­ stoffzellen bereitzustellen. Die Anlage weist einen Reformie­ rungsreaktor 1 auf, der aus einem eingangsseitig zugeführtem Wasserdampf/Methanol-Gemisch 2 ein Reformat 3 erzeugt und abgibt, das den gewünschten Wasserstoff enthält. Das Reformat 3 tritt als Gasstrom aus dem Reformierungsreaktor 1 aus. Zur Vermeidung, daß dem Reformat 3 ein unerwünschter Anteil an Kohlenmonoxid beigefügt ist, welcher beispielsweise eine nachgeschaltete PEM-Brennstoffzellenanordnung vergiften könnte, ist einem Reformer 1a des Reformierungsreaktors 1 eine CO-Oxidationsstufe 16 nachgeschaltet, in welcher Kohlenmonoxid in Kohlendioxid umwandelbar ist.The plant for water vapor reforming of methanol shown only with its presently relevant components in FIG. 1 can be used, for example, in a fuel cell-operated motor vehicle to provide hydrogen for supplying the fuel cells. The plant has a reforming reactor 1 , which generates and emits a reformate 3 from a water vapor / methanol mixture 2 supplied on the inlet side, which contains the desired hydrogen. The reformate 3 exits the reforming reactor 1 as a gas stream. To prevent the reformate 3 from having an undesirable proportion of carbon monoxide added, which could, for example, poison a downstream PEM fuel cell arrangement, a reformer 1 a of the reforming reactor 1 is followed by a CO oxidation stage 16 , in which carbon monoxide can be converted into carbon dioxide.

Das in den Reformierungsreaktor 1 eingeleitete Wasserdampf/Me­ thanol-Gemisch 2 wird in einer Gemischbereitungsstufe 4 her­ gestellt, wozu dieser Stufe 4 über eine Methanolzuführungslei­ tung 5 Methanol und über eine Wasserzuführungsleitung 6 Wasser zugeführt wird. Dabei können zuerst die flüssigen Komponenten gemischt und dann zusammen verdampft bzw. überhitzt oder alternativ zunächst die beiden Bestandteile getrennt verdampft und anschließend gemischt werden. Der Betrieb der Anlage wird von einer Steuer- oder Regeleinheit 7 gesteuert. Der Aufbau des Reformierungsreaktors 1, der Gemischbereitungsstufe 4 und der Steuer- oder Regeleinheit 7 entspricht hierbei herkömmlichen Realisierungen dieser Komponenten, so daß hierauf nicht näher eingegangen zu werden braucht.The introduced into the reforming reactor 1 steam / Me THANOL mixture 2 is provided in a mixture preparation stage 4 ago, to which this Level 4 tung 5 methanol over a Methanolzuführungslei and is supplied via a water supply pipe 6 water. The liquid components can first be mixed and then evaporated or overheated together, or alternatively the two components can first be evaporated separately and then mixed. The operation of the system is controlled by a control or regulating unit 7 . The structure of the reforming reactor 1 , the mixture preparation stage 4 and the control or regulating unit 7 corresponds to conventional implementations of these components, so that there is no need to go into further detail here.

Wie beispielsweise aus dem Stand der Technik bekannt ist, sind der Reformer 1a, in welchem eine endotherme Reaktion statt­ findet, und die CO-Oxidationsstufe 1b, in welcher eine exo­ therme Reaktion stattfindet, direkt miteinander gekoppelt. Eine Luftzudosierung, welche beispielsweise dem Wasserdampf/Me­ thanol-Gemisch 2 zugebbar ist, ist nicht im einzelnen dargestellt.As is known, for example, from the prior art, the reformer 1 a, in which an endothermic reaction takes place, and the CO oxidation stage 1 b, in which an exothermic reaction takes place, are directly coupled to one another. Air metering, which can be added to the water vapor / methanol mixture 2, for example, is not shown in detail.

Die Steuer- und Regeleinheit 7 empfängt, beispielsweise über einen Sensor 9, ein Temperatursignal, welches die Temperatur des aus dem Reformierungsreaktor 1 austretenden Reformat- bzw. Gasgemischstromes darstellt. Entsprechend dem ermittelten Temperatursignal gibt die Steuer- oder Regeleinheit 7 über eine Leitung 8 ein Signal an die Gemischbereitungsstufe 4, durch welches das Mischungsverhältnis des von der Gemischbereitungs­ stufe 4 erzeugten Eduktstromes (Wasser/Methanol-Verhältnis) variierbar ist.The control and regulating unit 7 receives, for example via a sensor 9 , a temperature signal which represents the temperature of the reformate or gas mixture stream emerging from the reforming reactor 1 . Accordingly, the temperature signal detected is the control or regulating unit 7 via a line 8 a signal to the mixture preparation stage 4, by means of which the mixing ratio of is from the mixture preparation Tung level 4 feed stream generated (water / methanol ratio) varied.

Beispielsweise kann mittels der Gemischbereitungsstufe 4 eine Erniedrigung des Wasserstoff/Methanol-Verhältnisses (Erhöhung des Methanolanteils) bewirkt werden. Eine derartige Ernied­ rigung des Wasserstoff/Methanol-Verhältnisses führt dazu, daß am Ausgang des Reformers 1a eine höhere CO-Konzentration vor­ liegt. Ursache hierfür ist das Wassergas-Shift-Gleichgewicht.For example, the mixture preparation stage 4 can bring about a reduction in the hydrogen / methanol ratio (increase in the proportion of methanol). Such a reduction of the hydrogen / methanol ratio leads to a higher CO concentration being present at the exit of the reformer 1 a. The reason for this is the water gas shift balance.

Diese erhöhte CO-Konzentration liegt somit am Eingang der CO- Oxidationsstufe 1b vor. Insgesamt verschiebt sich hierdurch das Temperaturprofil des Gesamtsystems Reformer-CO-Oxidations­ stufe stromabwärts, d. h. das Temperaturprofil verschiebt sich im vorderen Teil des Gesamtsystems zu niedrigeren, im hinteren Teil des Gesamtsystems zu höheren Temperaturen. Insgesamt wird hierdurch ein gleichmäßigeres Temperaturprofil erreicht, wo­ durch Alterungseffekte, welche bei herkömmlichen Reaktoren auftraten, wesentlich vermindert werden können. Durch die beschriebene Erniedrigung des Wasser/Methanol-Verhältnisses kann ferner der Systemwirkungsgrad wirksam erhöht werden.This increased CO concentration is therefore present at the entrance to CO oxidation state 1 b. Overall, this shifts the temperature profile of the overall system reformer CO oxidation stage downstream, ie the temperature profile shifts to lower temperatures in the front part of the overall system and higher temperatures in the rear part of the overall system. Overall, this results in a more uniform temperature profile, where aging effects, which occurred in conventional reactors, can be significantly reduced. The described lowering of the water / methanol ratio can also effectively increase the system efficiency.

Mit der erfindungsgemäßen Vorgehensweise ist es insbesondere möglich, eine alterungsbedingte Verschiebung des Temperatur­ profils des Gesamtsystems (alterungsbedingte Verschiebung des Temperaturprofils zur Eingangsseite hin) wirksam zu kompen­ sieren. Wird nämlich durch die Steuer- oder Regeleinheit 7, welche insbesondere als Temperaturcontroller ausgebildet sein kann, eine niedrigere Temperatur des aus der CO-Oxidationsstufe 1b austretenden Gasgemisches festgestellt, welche für die alterungsbedingte Verschiebung des Temperaturprofils charakteristisch ist, kann durch entsprechende Änderung des Mischungsverhältnisses in der Gemischbereitungsstufe 4 dieser Temperaturerniedrigung an der Ausgangsseite des Systems entgegengewirkt werden, wie bereits beschrieben wurde. Die alterungsbedingte Verschiebung des Temperaturprofils bewirkt insbesondere eine Beeinträchtigung der Umsatzleistung der beiden Reaktorkomponenten, d. h. des Reformers 1a sowie der CO- Oxidationsstufe 1b. Insgesamt stellen daher die Steuer- oder Regeleinheit 7, die Gemischbereitungsstufe 4, der Reaktor 1 sowie der Temperatursensor 9 einen Regelkreis zur Regelung des aus der CO-Oxidationsstufe bzw. dem Reaktor 1 austretenden Gasgemisches dar.With the procedure according to the invention, it is in particular possible to effectively compensate for an age-related shift in the temperature profile of the overall system (age-related shift in the temperature profile towards the input side). If the control or regulating unit 7 , which can be designed in particular as a temperature controller, determines a lower temperature of the gas mixture emerging from the CO oxidation stage 1 b, which is characteristic of the age-related shift in the temperature profile, can be changed by changing the mixing ratio in the mixture preparation stage 4 of this temperature reduction can be counteracted on the output side of the system, as has already been described. The aging-related shift in the temperature profile in particular has an adverse effect on the conversion performance of the two reactor components, ie the reformer 1 a and the CO oxidation state 1 b. Overall, the control or regulating unit 7 , the mixture preparation stage 4 , the reactor 1 and the temperature sensor 9 therefore constitute a control circuit for regulating the gas mixture emerging from the CO oxidation stage or the reactor 1 .

Claims (5)

1. Verfahren zum Betrieb einer Anlage zur Wasserdampf­ reformierung von Kohlenwasserstoffen, insbesondere Methanol, bei dem in einer Gemischbereitungsstufe (4) aus Wasser und wenigstens einem Kohlenwasserstoff ein Wasserdampf/Kohlen­ wasserstoff-Gemisch bereitet und das bereitete Wasserdampf/Kohlenwasserstoff-Gemisch in einen Reformierungsreaktor (1) eingeleitet wird, dadurch gekennzeichnet, daß das Wasserdampf/Kohlenwasserstoff-Mischungsverhältnis des in den Reformierungsreaktor (1) eingeleiteten Wasserdampf/Koh­ lenwasserstoff-Gemisches dermaßen eingestellt oder angepaßt wird, daß eine alterungsbedingte Verschiebung des Temperaturprofils innerhalb des Reformierungsreaktors kompensiert wird.1.Method for operating a system for water vapor reforming of hydrocarbons, in particular methanol, in which a water vapor / hydrocarbon mixture is prepared from water and at least one hydrocarbon in a mixture preparation step ( 4 ) and the water vapor / hydrocarbon mixture prepared in a reforming reactor ( 1 ) is initiated, characterized in that the water vapor / hydrocarbon mixture ratio of the introduced in the reforming reactor ( 1 ) water vapor / Koh lenwasserstoff mixture is adjusted or adjusted such that an aging-related shift in the temperature profile within the reforming reactor is compensated. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Wasserdampf/Kohlenwasserstoff-Mischungsverhältnis in Abhängig­ keit von der Temperatur des aus dem Reformierungsreaktor(1) austretenden Reformatgasstroms eingestellt wird.2. The method according to claim 1, characterized in that the water vapor / hydrocarbon mixture ratio is set as a function of the temperature of the reformate gas stream emerging from the reforming reactor ( 1 ). 3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß die Temperatur (T) des aus dem Reformierungsreaktor (1) austreten­ den Reformatgasstroms mittels der Einstellung des Wasserdampf/Koh­ lenwasserstoff-Mischungsverhältnisses auf einen konstanten Wert geregelt wird.3. The method according to claim 2, characterized in that the temperature (T) of the reforming reactor ( 1 ) emerging from the reformate gas stream is regulated to a constant value by means of the setting of the water vapor / carbon mixture ratio. 4. Anlage zur Durchführung des Verfahrens nach einem der Ansprüche 1 bis 3, mit einer Gemischbereitungsstufe (4) zur Bereitstellung eines Wasserdampf/Kohlenwasserstoff-Gemisches aus Wasser und Methanol, und einem Reformierungsreaktor (1), welcher insbesondere einen Reformer (1a) und eine CO-Oxida­ tionsstufe (1b) aufweist, welchem das Wasserdampf/Kohlen­ wasserstoff-Gemisch zugebbar ist, gekennzeichnet durch Mittel (7, 4) zur Einstellung bzw. Anpassung des Wasserdampf/Kohlen­ wasserstoff-Mischungsverhältnisses des dem Reformierungsreaktor (1) zugeführten Wasserdampf/Kohlenwasserstoff-Gemisches zur Kompensation einer alterungsbedingten Verschiebung eines Temperaturprofils innerhalb des Reformierungsreaktors (1).4. Plant for performing the method according to one of claims 1 to 3, with a mixture preparation stage ( 4 ) for providing a water vapor / hydrocarbon mixture of water and methanol, and a reforming reactor ( 1 ), which in particular a reformer ( 1 a) and has a CO-Oxida tion stage ( 1 b), to which the water vapor / carbon hydrogen mixture can be added, characterized by means ( 7 , 4 ) for adjusting or adjusting the water vapor / carbon hydrogen mixing ratio of the water vapor supplied to the reforming reactor ( 1 ) / Hydrocarbon mixture to compensate for an aging-related shift in a temperature profile within the reforming reactor ( 1 ). 5. Anlage nach Anspruch 4, gekennzeichnet durch stromabwärtig des Reformierungsreaktors (1) angeordnete Mittel (9) zur Be­ stimmung der Temperatur des aus dem Reformierungsreaktor (1) austretenden Reformatgasstroms und eine Steuer- und Regel­ einheit (7) zur Steuerung der Gemischbereitungsstufe (4), über welche ein geeignetes Wasserdampf/Kohlenwasserstoff-Mischver­ hältnis einstellbar ist.5. Plant according to claim 4, characterized by downstream of the reforming reactor ( 1 ) arranged means ( 9 ) for determining the temperature of the reforming reactor ( 1 ) emerging reformate gas stream and a control unit ( 7 ) for controlling the mixture preparation stage ( 4th ), by means of which a suitable water vapor / hydrocarbon mixture ratio can be set.
DE19918997A 1999-04-27 1999-04-27 Process for operating a plant for steam reforming of hydrocarbons, in particular methanol, and corresponding plant Expired - Fee Related DE19918997C2 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
DE19918997A DE19918997C2 (en) 1999-04-27 1999-04-27 Process for operating a plant for steam reforming of hydrocarbons, in particular methanol, and corresponding plant
JP2000613560A JP3782665B2 (en) 1999-04-27 2000-02-15 Method of operating a steam reforming plant of hydrocarbons, in particular methanol, and corresponding plant
PCT/EP2000/001225 WO2000064576A1 (en) 1999-04-27 2000-02-15 Method for operating a system for the water vapor reformation of hydrocarbons, especially methanol, and a corresponding system
DE50013776T DE50013776D1 (en) 1999-04-27 2000-02-15 METHOD OF OPERATING A PLANT FOR THE WATER VAPOR REFORMIFICATION OF HYDROCARBONS OR METHANOL
EP00906329A EP1173274B1 (en) 1999-04-27 2000-02-15 Method for operating a system for the water vapor reformation of hydrocarbons, especially methanol
US09/984,339 US7377950B2 (en) 1999-04-27 2001-10-29 Method for operating a plant for the steam reforming of hydrocarbons and corresponding plant

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19918997A DE19918997C2 (en) 1999-04-27 1999-04-27 Process for operating a plant for steam reforming of hydrocarbons, in particular methanol, and corresponding plant

Publications (2)

Publication Number Publication Date
DE19918997A1 DE19918997A1 (en) 2000-11-02
DE19918997C2 true DE19918997C2 (en) 2001-06-07

Family

ID=7905950

Family Applications (2)

Application Number Title Priority Date Filing Date
DE19918997A Expired - Fee Related DE19918997C2 (en) 1999-04-27 1999-04-27 Process for operating a plant for steam reforming of hydrocarbons, in particular methanol, and corresponding plant
DE50013776T Expired - Lifetime DE50013776D1 (en) 1999-04-27 2000-02-15 METHOD OF OPERATING A PLANT FOR THE WATER VAPOR REFORMIFICATION OF HYDROCARBONS OR METHANOL

Family Applications After (1)

Application Number Title Priority Date Filing Date
DE50013776T Expired - Lifetime DE50013776D1 (en) 1999-04-27 2000-02-15 METHOD OF OPERATING A PLANT FOR THE WATER VAPOR REFORMIFICATION OF HYDROCARBONS OR METHANOL

Country Status (5)

Country Link
US (1) US7377950B2 (en)
EP (1) EP1173274B1 (en)
JP (1) JP3782665B2 (en)
DE (2) DE19918997C2 (en)
WO (1) WO2000064576A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10238988A1 (en) * 2002-08-20 2004-03-04 Viessmann Werke Gmbh & Co Kg Method for operating an apparatus for generating hydrogen and apparatus for generating hydrogen
DE102005058530A1 (en) * 2005-12-08 2007-07-26 J. Eberspächer GmbH & Co. KG Reformeranordnung, functional system of reformer assembly and hydrogen-consuming system and method of operating a reformer assembly

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10054846A1 (en) 2000-11-04 2002-08-08 Xcellsis Gmbh Method of operating a gas generating device and gas generating device
DE10061035A1 (en) 2000-12-08 2002-06-13 Fev Motorentech Gmbh Injection device for the metered injection of two liquids in a reaction chamber
EP1348481A1 (en) * 2002-03-27 2003-10-01 Sulzer Hexis AG Process for regulating the reactions between at least two gaseous components
US7541007B2 (en) * 2002-12-20 2009-06-02 Lehigh University Microreactor and method of use to produce hydrogen by methanol reforming
KR100551036B1 (en) * 2004-06-30 2006-02-13 삼성에스디아이 주식회사 Reformer for fuel cell system and fuel cell system having the same
DE102010050901A1 (en) * 2010-11-10 2012-05-10 Enymotion Gmbh Method for operating a fuel cell system
CN110155945B (en) * 2019-04-22 2020-12-25 浙江大学 Self-heating methanol reforming hydrogen production reactor integrating CO selective methanation

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1949184B2 (en) * 1968-11-19 1974-09-19 United Aircraft Corp., East Hartford, Conn. (V.St.A.) Method for regulating the inflow of the reactants of a converter in which fuel for operating a fuel element is generated
DE2157722C2 (en) * 1970-12-31 1982-07-01 United Technologies Corp., 06101 Hartford, Conn. Control system for a fuel cell
DE19623919C1 (en) * 1996-06-15 1997-12-11 Daimler Benz Ag Process for operating a plant for steam reforming of methanol
DE19623937C1 (en) * 1996-06-15 1997-12-11 Daimler Benz Ag Process for operating a plant for steam reforming of methanol

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5498487A (en) * 1994-08-11 1996-03-12 Westinghouse Electric Corporation Oxygen sensor for monitoring gas mixtures containing hydrocarbons
DE19544895C1 (en) * 1995-12-01 1997-02-27 Daimler Benz Ag Oxidising carbon mon:oxide in gas mixt. from hydrocarbon reforming plant
JPH09315801A (en) * 1996-03-26 1997-12-09 Toyota Motor Corp Fuel reforming method, fuel reformer and fuel-cell system provided with the reformer
JP3870455B2 (en) * 1996-09-27 2007-01-17 トヨタ自動車株式会社 Carbon monoxide concentration reducing device and method, and fuel cell power generator
JPH11255512A (en) * 1998-03-09 1999-09-21 Toyota Motor Corp Apparatus for decreasing carbon monoxide and its driving
DE19847211C1 (en) 1998-10-13 2000-05-18 Dbb Fuel Cell Engines Gmbh Method for operating a reformer / CO oxidation unit

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1949184B2 (en) * 1968-11-19 1974-09-19 United Aircraft Corp., East Hartford, Conn. (V.St.A.) Method for regulating the inflow of the reactants of a converter in which fuel for operating a fuel element is generated
DE2157722C2 (en) * 1970-12-31 1982-07-01 United Technologies Corp., 06101 Hartford, Conn. Control system for a fuel cell
DE19623919C1 (en) * 1996-06-15 1997-12-11 Daimler Benz Ag Process for operating a plant for steam reforming of methanol
DE19623937C1 (en) * 1996-06-15 1997-12-11 Daimler Benz Ag Process for operating a plant for steam reforming of methanol

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10238988A1 (en) * 2002-08-20 2004-03-04 Viessmann Werke Gmbh & Co Kg Method for operating an apparatus for generating hydrogen and apparatus for generating hydrogen
DE10238988B4 (en) * 2002-08-20 2006-07-27 Viessmann Werke Gmbh & Co Kg Process for operating a hydrogen generating apparatus and apparatus for generating hydrogen
DE102005058530A1 (en) * 2005-12-08 2007-07-26 J. Eberspächer GmbH & Co. KG Reformeranordnung, functional system of reformer assembly and hydrogen-consuming system and method of operating a reformer assembly

Also Published As

Publication number Publication date
WO2000064576A1 (en) 2000-11-02
JP2002542143A (en) 2002-12-10
DE19918997A1 (en) 2000-11-02
US7377950B2 (en) 2008-05-27
JP3782665B2 (en) 2006-06-07
EP1173274A1 (en) 2002-01-23
EP1173274B1 (en) 2006-11-22
US20020053164A1 (en) 2002-05-09
DE50013776D1 (en) 2007-01-04

Similar Documents

Publication Publication Date Title
DE10059578B4 (en) Method for starting and stopping a methanol reforming device
EP0813262B1 (en) Process for operating a device for steam reforming of methanol
DE69816636T2 (en) CLEAN HYDROGEN
DE69912044T2 (en) Device and method for regulating a reformer
DE19727589B4 (en) Apparatus and method for starting the hydrogen-rich gas generating apparatus
DE10054139B4 (en) Process and apparatus for reforming a hydrocarbon for use in a fuel cell system
DE10393940T5 (en) Control of the fuel mixture for fuel cell power plants, which is operated with multiple fuels
DE19918997C2 (en) Process for operating a plant for steam reforming of hydrocarbons, in particular methanol, and corresponding plant
DE19727588C1 (en) Device for generating a hydrogen-rich and low-carbon monoxide gas
EP0813263B1 (en) Process for operating a device for steam reforming of methanol
DE19847211C1 (en) Method for operating a reformer / CO oxidation unit
WO2008031381A1 (en) Reformer
DE102004059494B4 (en) Method for determining an air ratio in a burner for a fuel cell heater and fuel cell heater
EP1213779B1 (en) Fuel cell system having an associated gas producing system
EP1427668B9 (en) Device for the generation of hydrogen
DE10237744A1 (en) Reactor system used in fuel cell-operated vehicles for producing hydrogen from hydrocarbons or hydrocarbon derivatives by autothermal reformation has temperature-controlled start-up burner for burning hydrocarbons with air
DE10136769A1 (en) Reformer unit for generating a reformate
DE102004001310A1 (en) Operating a steam reforming reactor for producing hydrogen for use in a fuel cell comprises a start-up phase in which the reactor is supplied with a hydrocarbon gas and flue gas from a gas burner
DE10349075B4 (en) Apparatus for supplying fuel to a burner in a fuel cell system with a reformer
DE10054842A1 (en) Process for electrical commissioning of a fuel cell
EP1207134B1 (en) Gas generating system for a reformer
DE10064441A1 (en) Setting operating temperature in reformer involves carrying out operating temperature regulation by setting quantity of at least one educt to be fed into reformer
DE10041384C1 (en) Method and device for generating a hydrogen-rich gas
DE10238988B4 (en) Process for operating a hydrogen generating apparatus and apparatus for generating hydrogen
DE102016123591A1 (en) Process for reforming fuel in an exhaust line of an internal combustion engine and internal combustion engine

Legal Events

Date Code Title Description
OP8 Request for examination as to paragraph 44 patent law
8127 New person/name/address of the applicant

Owner name: XCELLSIS GMBH, 70567 STUTTGART, DE

D2 Grant after examination
8364 No opposition during term of opposition
8327 Change in the person/name/address of the patent owner

Owner name: BALLARD POWER SYSTEMS AG, 70567 STUTTGART, DE

8327 Change in the person/name/address of the patent owner

Owner name: NUCELLSYS GMBH, 73230 KIRCHHEIM, DE

8339 Ceased/non-payment of the annual fee